4-Chloro­anilinium 2-carb­oxy­acetate

Zhao, M.-M.

doi:10.1107/S1600536812025469

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2079

https://doi.org/10.1107/S1600536812025469

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4-Chloroanilinium 2-carboxyacetate

Min-Min Zhao ^a ^*

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn

(Received 23 May 2012; accepted 5 June 2012; online 13 June 2012)

In the title molecular salt, C₆H₇ClN⁺·C₃H₃O₄⁻, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, leading to a two-dimensional network parallel to the bc plane. Weak C—H⋯O interactions are also observed.

Related literature

For the structures and properties of related compounds, see: Chen et al. (2001 ); Wang et al. (2002 ); Xue et al. (2002 ); Huang et al. (1999 ); Zhang et al. (2001 ); Ye et al. (2008 ).

Experimental

Crystal data

C₆H₇ClN⁺·C₃H₃O₄⁻
M_r = 231.63
Monoclinic, P 2₁ /c
a = 12.8272 (19) Å
b = 9.2273 (10) Å
c = 8.4114 (13) Å
β = 93.809 (2)°
V = 993.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 153 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
6935 measured reflections
2259 independent reflections
1985 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.06
2259 reflections
137 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O1ⁱ	0.82	1.71	2.5314 (14)	176
N1—H1B⋯O2ⁱⁱ	0.89	1.87	2.7546 (16)	176
N1—H1C⋯O4ⁱ	0.89	2.25	2.8702 (15)	127
N1—H1C⋯O2ⁱⁱⁱ	0.89	2.25	2.9313 (15)	133
N1—H1A⋯O3	0.89	1.91	2.7848 (15)	166
C3—H3A⋯O3	0.93	2.55	3.2599 (18)	134
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812025469/bx2414sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025469/bx2414Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025469/bx2414Isup3.cml

checkCIF report

Comment top

Simple organic salts containing strong intrermolecular H–bonds have attracted an attention as materials which display ferroelectric–paraelectric phase transitions (Chen et al., 2001; Huang et al., 1999; Zhang et al., 2001). With the purpose of obtaining phase transition crystals of organic salts, various organic molecules have been studied and a series of new crystal materials have been elaborated (Wang et al., 2002; Xue et al., 2002; Ye et al. ,2008). Herewith, we present the synthesis and crystal structure of the title compound, 4-chloroanilinium 2–carboxyacetate.

In the title compound (Fig. 1), the bond lengths and angles have normal values. The asymmetric unit contains one 4-chloroanilinium cation and one 2–carboxyacetate anion. The protonated N atom is involved in strong intramolecular N—H···O hydrogen bonds with the N···O distances of N1—H1A···O3 = 2.7848 (15)Å; N1—H1B···O2 = 2.7546 (16)Å, N1—H1C···O2 = 2.9313 (15)Å and N1—H1C···O4 = 2.8702 (15)Å. The N—H···O and O—H···O H–bonding interactions connected the components into a 2D network parallel to the bc–plane. A weak non–classical intermolecular C3—H3A···O3 interaction is observed , Table1.

Related literature top

For the structures and properties of related compounds, see: Chen et al. (2001); Wang et al. (2002); Xue et al. (2002); Huang et al. (1999); Zhang et al. (2001); Ye et al. (2008).

Experimental top

The malonic acid (10 mmol), 4-chloroaniline (10 mmol) and ethanol (50 mL) were added into a 100 mL flask. The mixture was stirred at 333 K for 2 h, and then the precipitate was filtrated out. Colourless crystals suitable for X–ray diffraction were obtained by slow evaporation of the solution.

Structure description top

For the structures and properties of related compounds, see: Chen et al. (2001); Wang et al. (2002); Xue et al. (2002); Huang et al. (1999); Zhang et al. (2001); Ye et al. (2008).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the asymmetric unit with the atomic numbering scheme. The displacement ellipsoids were drawn at the 30% probability level.

4-Chloroanilinium 2-carboxyacetate top

Crystal data top

C₆H₇ClN⁺·C₃H₃O₄⁻	F(000) = 480
M_r = 231.63	D_x = 1.549 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2259 reflections
a = 12.8272 (19) Å	θ = 2.7–27.5°
b = 9.2273 (10) Å	µ = 0.38 mm⁻¹
c = 8.4114 (13) Å	T = 153 K
β = 93.809 (2)°	Block, colourless
V = 993.4 (2) Å³	0.10 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	2259 independent reflections
Radiation source: fine-focus sealed tube	1985 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
CCD profile fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→11
T_min = 0.910, T_max = 1.000	l = −10→10
6935 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0471P)² + 0.2506P] where P = (F_o² + 2F_c²)/3
2259 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.32 e Å⁻³
4 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₆H₇ClN⁺·C₃H₃O₄⁻	V = 993.4 (2) Å³
M_r = 231.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8272 (19) Å	µ = 0.38 mm⁻¹
b = 9.2273 (10) Å	T = 153 K
c = 8.4114 (13) Å	0.10 × 0.05 × 0.05 mm
β = 93.809 (2)°

Data collection top

Rigaku Mercury CCD diffractometer	2259 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1985 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.025
6935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	4 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	Δρ_max = 0.32 e Å⁻³
2259 reflections	Δρ_min = −0.27 e Å⁻³
137 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.58798 (3)	0.24099 (5)	0.04636 (6)	0.03142 (14)
O1	0.05355 (8)	0.92647 (10)	0.25990 (11)	0.0154 (2)
O2	0.12165 (8)	1.07190 (10)	0.45291 (12)	0.0164 (2)
O3	0.16242 (8)	0.58923 (10)	0.41276 (12)	0.0176 (2)
O4	−0.00722 (7)	0.64921 (10)	0.40573 (11)	0.0150 (2)
H4	−0.0212	0.5744	0.3562	0.022*
N1	0.16273 (9)	0.31425 (13)	0.27635 (14)	0.0144 (3)
H1A	0.1611	0.3942	0.3353	0.022*
H1B	0.1469	0.2379	0.3348	0.022*
H1C	0.1165	0.3220	0.1930	0.022*
C9	0.09274 (11)	0.67518 (15)	0.43794 (15)	0.0125 (3)
C7	0.09565 (10)	0.95030 (15)	0.39848 (16)	0.0119 (3)
C4	0.26723 (10)	0.29563 (15)	0.22045 (15)	0.0137 (3)
C1	0.46232 (12)	0.26233 (17)	0.11081 (19)	0.0203 (3)
C8	0.11608 (11)	0.82132 (15)	0.51033 (16)	0.0139 (3)
H8A	0.1889	0.8233	0.5495	0.017*
H8B	0.0743	0.8332	0.6014	0.017*
C6	0.39676 (12)	0.14367 (17)	0.11557 (19)	0.0217 (3)
H6A	0.4186	0.0533	0.0817	0.026*
C5	0.29804 (12)	0.16053 (16)	0.17131 (17)	0.0186 (3)
H5A	0.2532	0.0816	0.1755	0.022*
C2	0.43096 (12)	0.39847 (17)	0.15827 (18)	0.0206 (3)
H2A	0.4755	0.4776	0.1531	0.025*
C3	0.33224 (11)	0.41483 (16)	0.21357 (17)	0.0174 (3)
H3A	0.3098	0.5054	0.2459	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0211 (2)	0.0287 (3)	0.0460 (3)	0.00583 (15)	0.01430 (18)	0.00397 (18)
O1	0.0212 (5)	0.0124 (5)	0.0121 (5)	0.0001 (4)	−0.0013 (4)	−0.0001 (4)
O2	0.0213 (5)	0.0111 (5)	0.0167 (5)	−0.0022 (4)	0.0002 (4)	−0.0015 (4)
O3	0.0179 (5)	0.0131 (5)	0.0219 (5)	0.0021 (4)	0.0030 (4)	−0.0023 (4)
O4	0.0165 (5)	0.0108 (5)	0.0171 (5)	0.0002 (4)	−0.0019 (4)	−0.0018 (4)
N1	0.0143 (5)	0.0126 (6)	0.0161 (6)	0.0000 (4)	−0.0005 (5)	−0.0010 (4)
C9	0.0177 (6)	0.0113 (7)	0.0086 (6)	0.0002 (5)	0.0012 (5)	0.0032 (5)
C7	0.0105 (6)	0.0126 (7)	0.0129 (6)	0.0013 (5)	0.0028 (5)	−0.0005 (5)
C4	0.0141 (6)	0.0146 (7)	0.0122 (6)	0.0012 (5)	−0.0005 (5)	0.0002 (5)
C1	0.0154 (7)	0.0235 (8)	0.0223 (7)	0.0046 (6)	0.0043 (6)	0.0032 (6)
C8	0.0164 (6)	0.0122 (7)	0.0126 (6)	0.0007 (5)	−0.0011 (5)	−0.0008 (5)
C6	0.0251 (8)	0.0154 (8)	0.0249 (8)	0.0049 (6)	0.0032 (6)	−0.0008 (6)
C5	0.0205 (7)	0.0142 (8)	0.0210 (7)	−0.0005 (5)	0.0000 (6)	−0.0006 (5)
C2	0.0187 (7)	0.0187 (8)	0.0245 (8)	−0.0026 (6)	0.0028 (6)	0.0023 (6)
C3	0.0187 (7)	0.0131 (7)	0.0203 (7)	0.0011 (5)	0.0003 (6)	−0.0016 (5)

Geometric parameters (Å, º) top

Cl1—C1	1.7455 (16)	C4—C5	1.379 (2)
O1—C7	1.2709 (16)	C4—C3	1.384 (2)
O2—C7	1.2488 (17)	C1—C6	1.383 (2)
O3—C9	1.2238 (17)	C1—C2	1.386 (2)
O4—C9	1.3149 (16)	C8—H8A	0.9700
O4—H4	0.8200	C8—H8B	0.9700
N1—C4	1.4598 (17)	C6—C5	1.388 (2)
N1—H1A	0.8900	C6—H6A	0.9300
N1—H1B	0.8900	C5—H5A	0.9300
N1—H1C	0.8900	C2—C3	1.386 (2)
C9—C8	1.5015 (19)	C2—H2A	0.9300
C7—C8	1.5289 (18)	C3—H3A	0.9300

C9—O4—H4	115.8	C9—C8—C7	115.35 (11)
C4—N1—H1A	109.5	C9—C8—H8A	108.4
C4—N1—H1B	109.5	C7—C8—H8A	108.4
H1A—N1—H1B	109.5	C9—C8—H8B	108.4
C4—N1—H1C	109.5	C7—C8—H8B	108.4
H1A—N1—H1C	109.5	H8A—C8—H8B	107.5
H1B—N1—H1C	109.5	C1—C6—C5	119.42 (14)
O3—C9—O4	124.03 (13)	C1—C6—H6A	120.3
O3—C9—C8	121.60 (12)	C5—C6—H6A	120.3
O4—C9—C8	114.37 (11)	C4—C5—C6	119.25 (14)
O2—C7—O1	125.35 (12)	C4—C5—H5A	120.4
O2—C7—C8	116.31 (11)	C6—C5—H5A	120.4
O1—C7—C8	118.34 (12)	C1—C2—C3	118.99 (14)
C5—C4—C3	121.36 (13)	C1—C2—H2A	120.5
C5—C4—N1	119.37 (12)	C3—C2—H2A	120.5
C3—C4—N1	119.25 (12)	C4—C3—C2	119.60 (13)
C6—C1—C2	121.38 (14)	C4—C3—H3A	120.2
C6—C1—Cl1	119.71 (12)	C2—C3—H3A	120.2
C2—C1—Cl1	118.91 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1ⁱ	0.82	1.71	2.5314 (14)	176
N1—H1B···O2ⁱⁱ	0.89	1.87	2.7546 (16)	176
N1—H1C···O4ⁱ	0.89	2.25	2.8702 (15)	127
N1—H1C···O2ⁱⁱⁱ	0.89	2.25	2.9313 (15)	133
N1—H1A···O3	0.89	1.91	2.7848 (15)	166
C3—H3A···O3	0.93	2.55	3.2599 (18)	134

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₇ClN⁺·C₃H₃O₄⁻
M_r	231.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	12.8272 (19), 9.2273 (10), 8.4114 (13)
β (°)	93.809 (2)
V (Å³)	993.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6935, 2259, 1985
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.06
No. of reflections	2259
No. of parameters	137
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.27

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1ⁱ	0.82	1.71	2.5314 (14)	175.5
N1—H1B···O2ⁱⁱ	0.89	1.87	2.7546 (16)	176.2
N1—H1C···O4ⁱ	0.89	2.25	2.8702 (15)	126.9
N1—H1C···O2ⁱⁱⁱ	0.89	2.25	2.9313 (15)	133.2
N1—H1A···O3	0.89	1.91	2.7848 (15)	165.7
C3—H3A···O3	0.93	2.55	3.2599 (18)	134

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) x, −y+3/2, z−1/2.

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

References

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